EP2868688B1 - Film de polyester - Google Patents
Film de polyester Download PDFInfo
- Publication number
- EP2868688B1 EP2868688B1 EP13841399.2A EP13841399A EP2868688B1 EP 2868688 B1 EP2868688 B1 EP 2868688B1 EP 13841399 A EP13841399 A EP 13841399A EP 2868688 B1 EP2868688 B1 EP 2868688B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- film
- thickness
- temperature
- resin
- polyester
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 229920006267 polyester film Polymers 0.000 title claims description 45
- 229920005989 resin Polymers 0.000 claims description 76
- 239000011347 resin Substances 0.000 claims description 76
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 70
- 229920001225 polyester resin Polymers 0.000 claims description 40
- 239000004645 polyester resin Substances 0.000 claims description 40
- 238000004064 recycling Methods 0.000 claims description 21
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 9
- 239000010954 inorganic particle Substances 0.000 claims description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 63
- 239000005020 polyethylene terephthalate Substances 0.000 description 63
- 238000000034 method Methods 0.000 description 45
- 230000000052 comparative effect Effects 0.000 description 43
- 238000003475 lamination Methods 0.000 description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 31
- 238000001816 cooling Methods 0.000 description 28
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 24
- 229920000728 polyester Polymers 0.000 description 20
- 238000005056 compaction Methods 0.000 description 19
- -1 poly(ethylene terephthalate) Polymers 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 15
- 238000010438 heat treatment Methods 0.000 description 15
- 239000000155 melt Substances 0.000 description 15
- 239000002994 raw material Substances 0.000 description 15
- 239000000377 silicon dioxide Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 11
- 239000000314 lubricant Substances 0.000 description 10
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 235000013361 beverage Nutrition 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 230000003362 replicative effect Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 238000007665 sagging Methods 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 2
- 241000692870 Inachis io Species 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- NZZFYRREKKOMAT-UHFFFAOYSA-N diiodomethane Chemical compound ICI NZZFYRREKKOMAT-UHFFFAOYSA-N 0.000 description 1
- 238000009820 dry lamination Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- DTQVDTLACAAQTR-DYCDLGHISA-N trifluoroacetic acid-d1 Chemical compound [2H]OC(=O)C(F)(F)F DTQVDTLACAAQTR-DYCDLGHISA-N 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
- B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
- B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
- B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
- B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
- B29K2067/003—PET, i.e. poylethylene terephthalate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/26—Scrap or recycled material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08J2367/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the hydroxy and the carboxyl groups directly linked to aromatic rings
Definitions
- the present invention relates to a polyester film containing a polyester resin obtained by recycling PET bottles. More particularly, the present invention relates to a polyester film containing a polyester resin obtained by recycling PET bottles and having low thermal shrinkage rate, high lamination strength, and slight unevenness in thickness.
- a film containing 0.5 mol% or more and 5 mol% or less of isophthalic acid is advantageous in that it easily provides sufficient lamination strength as compared with a poly(ethylene terephthalate) film containing 0 mol% of isophthalic acid, but its Nz is too high to improve lamination strength and reduce unevenness in thickness simultaneously. Accordingly, this technique cannot be employed as it is.
- the present invention has been made in view of the above problems of the conventional techniques. That is, it is an object of the present invention to provide a polyester film as mentioned below:
- Another object of the present invention is to provide an excellent polyester film containing a polyester resin obtained by recycling PET bottles without unevenness in lamination strength in the inside of the film.
- the present inventors have conducted extensive studies, and resultantly have completed the present invention. That is, the present invention is configured as follows.
- the polyester film containing a polyester resin obtained by recycling PET bottles according to the present invention has the following effects.
- FIG. 1 A schematic drawing showing one embodiment of the inside of an extruder in a film production facility in the present invention.
- a biaxial stretching method is not particularly limited, and a tubular method and a simultaneous biaxial stretching method may be employed. A successive biaxial stretching method is preferable.
- the lower limit of the intrinsic viscosity of the resin composing a film measured by measuring the film is preferably 0.64 dl/g, more preferably 0.65 dl/g. If the intrinsic viscosity is less than 0.64 dl/g, at the time of producing a film using a recycled resin derived from PET bottles, a decrease in the viscosity may sometimes result in an undesirable defect of uneven thickness since many of the recycled resins derived from PET bottles have an intrinsic viscosity exceeding 0.70. Further, coloration of the film may occur, and therefore, it is not preferable.
- the upper limit of the intrinsic viscosity is preferably 0.80 dl/g, more preferably 0.70 dl/g. If it exceeds 0.80 dl/g, the resin is difficult to be discharged out of an extruder and the productivity may be deteriorated, and therefore, it is not preferable.
- the lower limit of the thickness is preferably 8 ⁇ m, more preferably 10 ⁇ m, and still more preferably 12 ⁇ m. If the film is thinner than 8 ⁇ m, the strength as a film may be insufficient, and therefore, it is not preferable.
- the upper limit of the thickness is preferably 200 ⁇ m, more preferably 50 ⁇ m, and still more preferably 30 ⁇ m. If it exceeds 200 ⁇ m, the film is so thick that processing may become difficult.
- the lower limit of the thermal shrinkage rate in the lengthwise direction (sometimes referred to as MD) and in the transverse direction (sometimes referred to as TD) is preferably 0.1%, more preferably 0.3%. If it is less than 0.1%, the effect of improvement is saturated, and besides, the film sometimes becomes mechanically fragile, and therefore, it is not preferable.
- the upper limit of the thermal shrinkage rate is preferably 1.5%, more preferably 1.2%. If it exceeds 1.5%, pitch deviation may be caused due to the dimensional change at the time of processing such as printing, and therefore, it is not preferable. Further, ff it exceeds 1.5%, shrinkage in the width direction may occur due to the dimensional change at the time of processing such as printing, and therefore, it is not preferable.
- the lower limit of the refractive index in the thickness direction is preferably 1.493, more preferably 1.494. If it is less than 1.493, orientation is too high and desired lamination strength may not be obtained.
- the upper limit of the refractive index is preferably 1.4995, more preferably 1.498. If it exceeds 1.4995, the molecular orientation of the film is insufficient and mechanical characteristics may be insufficient, and therefore, it is not preferable.
- the lower limit of the lamination strength is preferably 4.0 N/15 mm, more preferably 4.5 N/15 mm, and still more preferably 5 N/15 mm. If it is less than 4.0 N/15 mm, in the case where the film is used for producing a bag, the laminate part tends to be separated easily, and therefore, it is not preferable.
- the upper limit of the lamination strength is preferably 20 N/15 mm, more preferably 15 N/15 mm, and still more preferably 10 N/15 mm. If it exceeds 20 N/15 mm, the film may be substantially broken at the time of peeling, and therefore, it is not so preferable.
- the appearance evaluation after the lamination is carried out by visually observing a sample after laminate separation.
- the evaluation is performed as follows.
- the ⁇ level means that there are no micro voids of the adhesive in the surface after separation: the ⁇ level means that there are micro voids in 10% or less of the total separated surface area: and the ⁇ level means that there are micro voids in more than 10% of the total separated surface area.
- the ⁇ level is preferable, and the ⁇ level is more preferable.
- the ⁇ level is not preferable since the appearance is poor after separation of the laminate part and the product value is deteriorated. In the case where the lamination strength is less than 4 N/15 mm, since the basic characteristics of the present invention are not satisfied, the film is not preferable even if it is on the ⁇ level.
- a recycled polyester resin derived from PET bottles containing an isophthalic acid component as an acid component.
- the crystallinity of a polyester used for PET bottles is controlled to improve the bottle appearance, and as a result, a polyester containing 10 mol% or less of an isophthalic acid component is used in some cases.
- a material containing an isophthalic acid component is used in some cases.
- the lower limit of the amount of a terephthalic acid component in all dicarboxylic acid components composing the polyester resin contained in the film is preferably 95 mol%, more preferably 96 mol%, still more preferably 96.5 mol%, and particularly preferably 97 mol%. If it is less than 95 mol%, crystallinity is deteriorated, so that the thermal shrinkage rate may increase, and it is not so preferable.
- the lower limit of the amount of the terephthalic acid component in the polyester resin contained in the film is preferably 99.5 mol%, more preferably 99 mol%.
- the lower limit of the amount of the isophthalic acid component in all the dicarboxylic acid components composing the polyester resin contained in the film is preferably 0.5 mol%, more preferably 0.7 mol%, still more preferably 0.9 mol%, and particularly preferably 1 mol%. Since many of recycled polyester resins derived from PET bottles contain an isophthalic acid component, an amount of the isophthalic acid component composing the polyester resin in the film of less than 0.5 mol% consequently makes it difficult to produce a polyester film containing a recycled resin at a high rate, and therefore, it is not so preferable.
- the upper limit of the amount of the isophthalic acid component in all the dicarboxylic acid components composing the polyester resin contained in the film is preferably 5 mol%, more preferably 4 mol%, still more preferably 3.5 mol%, and particularly preferably 3 mol%. If it exceeds 5 mol%, crystallinity is deteriorated, so that the thermal shrinkage rate may increase, and it is not so preferable. Adjustment of the content of the isophthalic acid component to be within the above-mentioned range makes production of a film excellent in lamination strength and shrinkage rate, and reduced in unevenness in thickness easy, and therefore, it is preferable.
- the upper limit of the intrinsic viscosity of the recycled resin derived from PET bottles is preferably 0.9 dl/g, more preferably 0.8 dl/g, still more preferably 0.77 dl/g, and particularly preferably 0.75 dl/g. If it exceeds 0.9 dl/g, the resin may become difficult to be discharged out of an extruder and the productivity may be deteriorated, and therefore, it is not so preferable.
- the lower limit of the content of the polyester resin obtained by recycling PET bottles relative to the film is preferably 50 wt.%, more preferably 65 wt.%, and still more preferably 75 wt.%. If it is less than 50 wt.%, the content is too low for utilization of the recycled resin, and it is not so preferable in terms of contribution to environmental preservation.
- the upper limit of the content of the polyester resin obtained by recycling PET bottles is preferably 95 wt.%, more preferably 90 wt.%, and still more preferably 85 wt.%. If it exceeds 95 wt.%, it is sometimes impossible to sufficiently add a lubricant or an additive such as inorganic particles for improving the function as a film, and therefore, it is not so preferable.
- a polyester resin obtained by recycling PET bottles may be used as a master batch (a resin to be contained in a high concentration) to be used in the case where a lubricant or an additive such as inorganic particles is added for improving the function as a film.
- inorganic lubricants such as silica, calcium carbonate, and alumina, and also organic lubricants are preferable, and silica and calcium carbonate are more preferable. These lubricants provide transparency and slippage.
- the lower limit of the lubricant content in the film is preferably 0.01 wt.%, more preferably 0.015 wt.%, and still more preferably 0.02 wt.%. If it is less than 0.01 wt.%, the slippage may be deteriorated.
- the upper limit of the lubricant content is preferably 1 wt.%, more preferably 0.2 wt.%, and still more preferably 0.1 wt.%. If it exceeds 1 wt.%, transparency may be deteriorated, and it is not so preferable.
- a method for producing the film of the present invention is not particularly limited, but the following production method is recommended. It is important to set a temperature suitable for melting and extruding a resin in an extruder.
- the basic idea is that (1) deterioration is suppressed by extrusion at a temperature as low as possible, since a polyester resin used for PET bottles contains an isophthalic acid component, and (2) a part for melting at a high temperature and high pressure is kept to sufficiently and evenly melt highly crystalline micro parts with high intrinsic viscosity. Addition of the isophthalic acid component leads to deterioration of the tacticity of a polyester and a decrease in the melting point.
- a recommended production method may be, for example, a method of using two extruders in tandem, a method of increasing the pressure in a filter part, or a method of using a screw with high shear force for part of screw equipment.
- Fig. 1 shows one embodiment of the inside of an extruder in a film production facility in the present invention.
- the screw 1 includes a supply part 4, a compaction part 5, and a measurement part 6 from the base to the tip end thereof.
- the compaction part 5 is a region where the distance between the screw 1 and the barrels 3 is gradually narrowed.
- the extruder is preferably contrived to sufficiently carry out melt-kneading in the compaction part 5 in which the shear force is high, and to avoid thermal deterioration in the supply part 4 and the measurement part 6, by setting the temperature in the supply part 4 and the measurement part 6 as low as possible and setting the temperature in the compaction part 5 high.
- the lower limit of the set temperature in the resin melting part (excluding the highest set temperature in the compaction part of the screw in the extruder) in the extruder is preferably 270°C, and the upper limit thereof is preferably 290°C. If it is less than 270°C, extrusion becomes difficult, and if it exceeds 290°C, the resin may be deteriorated, and therefore, it is not so preferable.
- the lower limit of the highest set temperature in the compaction part of the screw in the extruder is preferably 295°C.
- crystals with high melting points 260°C to 290°C
- an additive, a crystallization nucleating agent, and the like are added, and unevenness in the fine melting behavior is observed in the resin material. If the highest set temperature is less than 295°C, it becomes difficult to sufficiently melt them, and therefore, it is not so preferable.
- the upper limit of the highest set temperature in the compaction part of the screw in the extruder is preferably 310°C. If it exceeds 310°C, the resin may be deteriorated, and therefore, it is not so preferable.
- the lower limit of the time for the resin to pass the region at the highest set temperature in the compaction part of the screw in the extruder is preferably 10 sec., more preferably 15 sec. If it is shorter than 10 sec., the polyester resin used for PET bottles cannot be melted sufficiently, and therefore, it is not so preferable.
- the upper limit of the time is preferably 60 sec., more preferably 50 sec. If it exceeds 60 sec., the resin may be easily deteriorated, and therefore, it is not so preferable. It is made possible to obtain a film reduced in unevenness in thickness, foreign matters such as fish eyes, and coloration by setting an extruder in such ranges even if a large quantity of a polyester resin obtained by recycling PET bottles is used.
- a resin melted in the above-mentioned manner is extruded in a sheet-like form on a cooling roll, and thereafter biaxially stretched.
- the stretching method may be a simultaneous biaxial stretching method, but a successive biaxial stretching method is preferable. In the above-mentioned manner, it is made easy to satisfy both productivity and the quality required in the present invention.
- a method for stretching the film in the present invention is not particularly limited, but the following points are important.
- MD lengthwise direction
- TD transverse direction
- the stretch ratios and temperatures in the lengthwise direction (MD) stretching and transverse direction (TD) stretching are important. If the MD stretch ratio and temperature are improper, stretching force is not evenly applied, and the orientation of molecules is insufficient, which may result in an increase in unevenness in thickness or insufficiency of mechanical characteristics. Further, the film may be torn in the next TD stretching step, or unevenness in thickness may be increased extremely.
- a method for stretching the film in the lengthwise direction is preferably a roll stretching method or an IR heating method.
- the lower limit of the MD stretching temperature is preferably 100°C, more preferably 110°C, and still more preferably 120°C. If it is less than 100°C, even if a polyester resin with an intrinsic viscosity of 0.64 dl/g or more is stretched to orient molecules in the lengthwise direction, the film may be torn in the next transverse stretching step or an extreme thickness defect may be caused, and therefore, it is not preferable.
- the upper limit of the MD stretching temperature is preferably 140°C, more preferably 135°C, and still more preferably 130°C. If it exceeds 140°C, orientation of molecular chains may become insufficient and mechanical characteristics may become insufficient, and therefore, it is not so preferable.
- the lower limit of the MD stretch ratio is preferably 2.5 times, more preferably 3.5 times, and still more preferably 4 times. If it is less than 2.5 times, even if a polyester resin with an intrinsic viscosity of 0.64 dl/g or more is stretched to orient molecules in the lengthwise direction, the film may be torn in the next transverse stretching step or an extreme thickness defect may be caused, and therefore, it is not so preferable.
- the upper limit of the MD stretch ratio is preferably 5 times, more preferably 4.8 times, and still more preferably 4.5 times. If it exceeds 5 times, the effect of improving mechanical strength and unevenness in thickness may be saturated, and it is not so meaningful.
- An MD stretching method may be the above-mentioned one-stage stretching, but the film is preferably stretched in two or more stages. Stretching in two or more stages makes it possible to well stretch a polyester resin with high intrinsic viscosity derived from a recycled resin containing isophthalic acid, and to reduce the unevenness in thickness and improve lamination strength and mechanical characteristics.
- the lower limit of the MD stretching temperature in the first stage is preferably 110°C, more preferably 115°C. If it is less than 110°C, heat is insufficient, so that vertical stretching cannot be carried out sufficiently and the film becomes poor in the flatness, and therefore, it is not preferable.
- the upper limit of the MD stretching temperature in the first stage is preferably 125°C, more preferably 120°C. If it exceeds 125°C, orientation of molecular chains may become insufficient and mechanical characteristics may be deteriorated, and therefore, it is not so preferable.
- the lower limit of the MD stretch ratio in the first stage is preferably 1.1 times, more preferably 1.3 times. If it is 1.1 times or more, a polyester resin with an intrinsic viscosity of 0.64 dl/g or more can be finally stretched in the lengthwise direction sufficiently by carrying weak stretching in the first stage, and accordingly, the productivity can be improved.
- the upper limit of the MD stretch ratio in the first stage is preferably 2 times, more preferably 1.6 times. If it exceeds 2 times, since the orientation of molecular chains in the lengthwise direction is so high that the stretching may become difficult in the second stage or thereafter and the film may have large unevenness in thickness, and therefore, it is not preferable.
- the lower limit of the MD stretching temperature in the second stage (or final stage) is preferably 110°C, more preferably 115°C. If it is 110°C or more, a polyester resin with an intrinsic viscosity of 0.64 or more can be sufficiently stretched in the lengthwise direction and can be stretched in the transverse direction in the next step, so that the unevenness in thickness in the lengthwise and transverse directions may be reduced.
- the upper limit of the MD stretching temperature is preferably 130°C, more preferably 125°C. If it exceeds 130°C, crystallization is promoted, so that the transverse stretching may become difficult or the unevenness in thickness may become significant, and therefore, it is not so preferable.
- the lower limit of the MD stretch ratio in the second stage (or final stage) is preferably 2.1 times, more preferably 2.5 times. If it is less than 2.1 times, even if a polyester resin with an intrinsic viscosity of 0.64 or more is stretched to orient molecules in the lengthwise direction, the film may be torn in the next transverse stretching step or an extreme thickness defect may be caused, and therefore, it is not so preferable.
- the upper limit of the MD stretch ratio is preferably 3.5 times, more preferably 3.1 times. If it exceeds 3.5 times, since the orientation in the lengthwise direction is so high that the stretching may be impossible in the second stage or thereafter and the film may have significant unevenness in thickness, and therefore, it is not so preferable.
- the lower limit of the TD stretching temperature is preferably 110°C, more preferably 120°C, and still more preferably 125°C. If it is less than 110°C, the stretching stress in the transverse direction is increased, so that the film may be torn or the unevenness in thickness may become extremely large, and therefore, it is not so preferable.
- the upper limit of the TD stretching temperature is preferably 150°C, more preferably 145°C, and still more preferably 140°C. If it exceeds 150°C, orientation of molecular chains does not increase, so that mechanical characteristics may be deteriorated, and therefore, it is not so preferable.
- the lower limit of the transverse direction (TD) stretch ratio is preferably 3.5 times, more preferably 3.9 times. If it less than 3.5 times, molecular orientation is weak and mechanical strength may become insufficient, and therefore, it is not so preferable. Further, the orientation of molecular chains in the lengthwise direction is significant and the balance between the lengthwise and transverse directions is deteriorated to make the unevenness in thickness large, and therefore, it is not so preferable.
- the upper limit of the TD stretch ratio is preferably 5.5 times, more preferably 4.5 times. If it exceeds 5.5 times, the film may be torn, and it is not so preferable.
- the film of the present invention it is desirable to properly set the conditions for heat fixation carried out in a tenter after the completion of the TD stretching and for the subsequent cooling of the film to room temperature.
- a polyester film containing a recycled resin derived from PET bottles and containing isophthalic acid has low crystallinity, tends to be melted in an ultra-fine level, and is poor in mechanical strength.
- the present invention is not limited to this method, and other recommended methods include a method of controlling the film tension correspondingly to the velocity of hot air in the tenter and the temperatures in the respective zones; a method of carrying out heat treatment at a relatively low temperature in a furnace with a sufficient length after completion of the stretching; and a method of relaxing the film by heat rolls after completion of the heat fixation.
- the lower limit of the temperature in the heat fixation 1 is preferably 160°C, more preferably 170°C. If it is less than 160°C, the thermal shrinkage rate becomes significant finally and deviation and shrinkage may be caused at the time of processing, and therefore, it is not so preferable.
- the upper limit of the temperature in the heat fixation 1 is preferably 215°C, more preferably 210°C. If it exceeds 215°C, the film is abruptly exposed to a high temperature, so that the unevenness in thickness becomes significant or the film may be torn, and therefore, it is not so preferable.
- the lower limit of the time for the heat fixation 1 is preferably 0.5 sec., more preferably 2 sec. If it is shorter than 0.5 sec, the film temperature increase may be insufficient.
- the upper limit of the time for the heat fixation 1 is preferably 10 sec., more preferably 8 sec. If it exceeds 10 sec., productivity may be deteriorated, and it is not so preferable.
- the lower limit of the temperature in the heat fixation 2 is preferably 220°C, more preferably 227°C. If it is less than 220°C, the thermal shrinkage rate becomes significant, and deviation and shrinkage may be caused at the time of processing, and therefore, it is not so preferable.
- the upper limit of the temperature in the heat fixation 2 is preferably 240°C, more preferably 237°C. If it exceeds 240°C, the film may be melted, or even if not melted, the film may be fragile, and therefore, it is not so preferable.
- the lower limit of the time for the heat fixation 2 is preferably 0.5 sec., more preferably 3 sec. If it is shorter than 0.5 sec., the film may be easily torn at the time of heat fixation, and therefore, it is not so preferable.
- the upper limit of the time for the heat fixation 2 is preferably 10 sec., more preferably 8 sec. If it exceeds 10 sec., sagging may occur and it may result in unevenness in thickness, and therefore, it is not so preferable.
- the lower limit of the temperature in the case where the heat fixation 3 is carried out as necessary is preferably 205°C, more preferably 220°C. If it is less than 205°C, the thermal shrinkage rate becomes significant, and deviation and shrinkage may be caused at the time of processing, and therefore, it is not so preferable.
- the upper limit of the temperature in the heat fixation 3 is preferably 240°C, more preferably 237°C. If it exceeds 240°C, the film may be melted, or even if not melted, the film may be fragile, and therefore, it is not so preferable.
- the lower limit of the time in the case where the heat fixation 3 is carried out as necessary is preferably 0.5 sec., more preferably 3 sec. If it is shorter than 0.5 sec., the film may be easily torn at the time of heat fixation, and therefore, it is not so preferable.
- the upper limit of the time for the heat fixation 3 is preferably 10 sec., more preferably 8 sec. If it exceeds 10 sec., sagging may occur and it may result in unevenness in thickness, and therefore, it is not so preferable.
- TD relaxation may be carried out at any point in the heat fixation.
- the lower limit thereof is preferably 0.5%, more preferably 3%. If it is less than 0.5%, the thermal shrinkage rate particularly in the transverse direction becomes significant, and deviation and shrinkage may be caused at the time of processing, and therefore, it is not so preferable.
- the upper limit thereof is preferably 10%, more preferably 8%. If it exceeds 10%, sagging may occur and it may result in unevenness in thickness, and therefore, it is not so preferable.
- the lower limit of the gradual cooling temperature after the TD heat fixation is preferably 90°C, more preferably 100°C. If it is less than 90°C, since the film contains isophthalic acid, the unevenness in thickness may become significant because of shrinkage by abrupt temperature change or the film may be torn, and therefore, it is not so preferable.
- the upper limit of the gradual cooling temperature is preferably 150°C, more preferably 140°C. If it exceeds 150°C, a sufficient cooling effect may not be caused, and therefore, it is not so preferable.
- the lower limit of the gradual cooling time after the heat fixation is preferably 2 sec., more preferably 4 sec. If it is shorter than 2 sec., a sufficient gradual cooling effect may not be caused, and therefore, it is not so preferable.
- the upper limit is preferably 20 sec., more preferably 15 sec. If it exceeds 20 sec., it is sometimes disadvantageous in terms of productivity, and therefore, it is not so preferable.
- a sample solution was prepared by dissolving a sample in a solvent mixture of chloroform D (manufactured by Yurisoppu Co., Ltd.) and trifluoroacetic acid D1 (manufactured by Yurisoppu Co., Ltd.) at 10 : 1 (volume ratio).
- NMR GEMINI-200 manufactured by Varian
- protons in the obtained sample solution were measured by NMR under the conditions of a temperature of 23°C and a number of integrations of 64. In the NMR measurement, a prescribed peak intensity of protons was calculated, and the content (mol%) of the terephthalic acid component and the isophthalic acid component in 100 mol% of acid components was calculated.
- the refractive index (Nz) in the thickness direction was measured according to JIS K 7105 using an Abbe's refractometer (manufactured by ATAGO Co., Ltd.). Sodium D ray was employed as a light source, a test piece with a refractive index of 1.74 was used, and methylene iodide was used as an intermediate liquid.
- the produced biaxially stretched polyester film and a polyethylene film were laminated using a urethane type adhesive (TM 569, CAT 10L, and ethyl acetate at 33.6 : 4.0 : 62.4 (weight ratio) manufactured by Toyo-Morton, Ltd.) by a dry lamination method and aged at 40°C for 4 days to obtain a laminate for lamination strength evaluation.
- the lamination conditions were a line velocity of 20 m/min, a drier temperature of 80°C, and an application amount after drying of 3 g/m 2 .
- the laminate was cut into a specimen having a size of 15 mm in width and 200 mm in length, and the peel strength (N/15 mm) at the interface between the untreated surface of the polyester film and the polyolefin resin layer was measured under the conditions of a temperature of 23°C and a relative humidity of 65% by using Tensilon model UMT-II-500 manufactured by Toyo Baldwin. The tensile speed was 20 cm/min and the peel angle was 180 degrees.
- the sample after the evaluation of (6) was visually observed.
- the o level means that there are no micro voids of the adhesive in the surface after separation:
- the ⁇ level means that there are micro voids in 10% or less of the total separated surface area: and the ⁇ level means that there are micro voids in more than 10% of the total separated surface area.
- a recycled polyester raw material was obtained by washing PET bottles for beverages to remove foreign matters such as the remaining beverage, thereafter melting the flakes obtained by pulverizing the PET bottles by an extruder, further changing the filter with a filter having a smaller mesh size, then separating the fine foreign matters by filtration twice, and then separating the fine foreign matters by third filtration using a filter with the smallest mesh size of 50 ⁇ m.
- the resin was named as a polyester A.
- the respective raw materials were dried at 125°C under a reduced pressure of 33 Pa for 8 hours. These raw materials were mixed in a manner that A/B/C became 70/20/10 (weight ratio) and charged into a uniaxial extruder.
- the temperature was set so as to keep the resin temperature at 280°C from the extruder to a melt line, a filter, and a T-die.
- the temperature was set so as to adjust the resin temperature to 305°C for 30 seconds from the starting point of a compaction part of a screw of the extruder and thereafter to 280°C again.
- the melt extruded out of the T-die was attached closely to a cooling roll to obtain an unstretched sheet. Then, the unstretched sheet was stretched (MD1) 1.41 times in the lengthwise direction with rolls heated to 118°C and having different circumferential speeds, and further stretched (MD2) 2.92 times in the lengthwise direction with rolls heated to 128°C and having different circumferential speeds. The vertically stretched sheet was led to a tenter, preheated at 121°C, and thereafter transversely stretched 4.3 times at 131°C.
- the sheet was subjected to treatment at 180°C without relaxation (0%) for 2.5 seconds (TS1), thereafter to treatment at 231°C with 5% of relaxation for 3.0 seconds (TS2), and further to treatment at 222°C without relaxation for 2.5 seconds (TS3). Then, the sheet was cooled in the same tenter at 120°C for 6 seconds and finally wound with a winder to obtain a biaxially stretched polyester film having a thickness of 18 ⁇ m.
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 1, except that the polyester raw materials were mixed in a manner that A/B/C could be 80/10/10 (weight ratio).
- a biaxially stretched polyester film was obtained by the same method as that in Example 2, except that the resin temperature was set at 305°C for 45 seconds from the starting point in the compaction part of the screw in the extruder and the final thickness of the film was changed to 12 ⁇ m.
- a recycled polyester raw material was obtained by washing PET bottles for beverages different from those in Example 1 to remove foreign matters such as the remaining beverage, thereafter melting the flakes obtained by pulverizing the PET bottles by an extruder, further changing the filter with a filter having a smaller mesh size, then separating the fine foreign matters by filtration twice, and then separating the fine foreign matters by third filtration using a filter with the smallest mesh size of 50 ⁇ m.
- the resin was named as a polyester D.
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 1, except that the polyester raw materials were mixed in a manner that D/B/C could be 60/30/10 (Example 4) and 80/10/10 (Example 5).
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 2, except that the film was subjected to treatment at 231°C with 5% of relaxation for 3.0 seconds (TS2), and then to treatment at 222°C without relaxation for 2.5 seconds (TS3) as heat fixation after completion of transverse stretching, and TS1 and the cooling step were not performed.
- TS2 231°C with 5% of relaxation for 3.0 seconds
- TS3 222°C without relaxation for 2.5 seconds
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 2, except that the resin temperature was set at 280°C in the entire region from the extruder to the melt line, the filter, and the T-die.
- the resin was named as a polyester E.
- the temperature was set so as to keep the resin temperature at 280°C from the extruder to the melt line, the filter, and the T-die.
- the temperature was set so as to adjust the resin temperature to 305°C for 90 seconds from the starting point of the compaction part of the screw of the extruder and thereafter to 280°C again.
- the film production conditions for the film were heating to 100°C by roll groups and an infrared heater, and thereafter vertical stretching 4.1 times by roll groups with different circumferential speeds, and then transverse stretching 4.2 times at 130°C.
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 2, except that the film was subjected to treatment at 229°C without relaxation for 2.6 seconds (TS2) and then to treatment at 200°C with 6.0% of relaxation for 2.5 seconds as heat fixation, and TS1 and the cooling step were not performed.
- TS2 229°C without relaxation for 2.6 seconds
- the temperature was set so as to keep the resin temperature at 280°C from the extruder to the melt line, the filter, and the T-die.
- the temperature was set so as to adjust the resin temperature to 305°C for 90 seconds from the starting point of the compaction part of the screw of the extruder and thereafter to 280°C again.
- the melt extruded out of the T-die was attached closely to a cooling roll to obtain an unstretched sheet. Then, the unstretched sheet was stretched (MD1) 1.2 times in the lengthwise direction with rolls heated to 110°C and having different circumferential speeds and further stretched (MD2) 2.8 times in the lengthwise direction with rolls heated to 120°C and having different circumferential speeds.
- the vertically stretched sheet was led to a tenter, preheated at 100°C, and thereafter transversely stretched 3.9 times at 105°C.
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 2, except that the film was subjected to treatment at 228°C without relaxation for 3.0 seconds (TS2) and then to treatment at 228°C with 5.0% of relaxation for 2.5 seconds as heat fixation, and TS1 and the cooling step were not performed.
- the resin was named as a polyester F.
- Polyester raw materials were mixed in a manner that F/B/C could be 80/10/10 (weight ratio), and the resin temperature was set at 310°C in the entire region from the extruder to the melt line, the filter, and the T-die. The melt extruded out of the T-die was attached closely to a cooling roll to obtain an unstretched sheet.
- the unstretched sheet was stretched (MD1) 1.6 times in the lengthwise direction with rolls heated to 126°C and having different circumferential speeds, further stretched (MD2) 1.3 times in the lengthwise direction with rolls heated to 126°C and having different circumferential speeds, and further stretched (MD3) 2.3 times in the lengthwise direction with rolls heated to 118°C and having different circumferential speeds.
- MD1 1.6 times in the lengthwise direction with rolls heated to 126°C and having different circumferential speeds
- MD2 further stretched
- MD3 2.3 times in the lengthwise direction with rolls heated to 118°C and having different circumferential speeds.
- the vertically stretched sheet was led to a tenter, preheated at 110°C, and thereafter transversely stretched 4.6 times at 120°C.
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 2, except that the film was thereafter subjected to treatment at 205°C without relaxation for 5.0 seconds (TS2) as heat fixation, and TS1, TS3 and the cooling step were not performed.
- TS2 5.0 seconds
- the temperature was set so as to keep the resin temperature at 280°C from the extruder to the melt line, the filter, and the T-die.
- the temperature was set so as to adjust the resin temperature to 300°C for 70 seconds from the starting point of the compaction part of the screw of the extruder and thereafter to 280°C again.
- the melt extruded out of the T-die was attached closely to a cooling roll to obtain an unstretched sheet. Then, the unstretched sheet was stretched (MD1) 3.9 times in the lengthwise direction with rolls heated to 107°C and having different circumferential speeds.
- the vertically stretched sheet was led to a tenter and preheated at 105°C and 115°C for 2 seconds each, respectively, and thereafter transversely stretched finally 4.1 times in 4 stretching zones of 120°C, 130°C, 145°C, and 155°C for 2 seconds, respectively. Then, for heat fixation, the sheet was subjected to treatment at 220°C without relaxation (0%) for 2.0 seconds (TS1), thereafter to treatment at 235°C without relaxation for 2.0 seconds (TS2), and further to treatment at 195°C with 2.0% of relaxation for 2.5 seconds (TS3).
- a biaxially stretched polyester film having a thickness of 18 ⁇ m was obtained by the same method as that in Example 2, except that no cooling step was performed and the sheet was finally wound with a winder.
- a biaxially stretched PET film was obtained by the same method as that in Comparative Example 7, except that the final thickness was changed to 31 ⁇ m.
- the biaxially stretched PET films obtained in Examples 1 to 5 were reduced in the unevenness in thickness and were excellent in lamination strength, and had good appearance after lamination.
- Comparative Example 1 since there was no TS1 and no cooling step, the unevenness in thickness was significant because of shrinkage or the like due to abrupt temperature change. In the case of Comparative Example 2, since the temperature in the compaction part of the screw was low, the resin was melted insufficiently and the unevenness in thickness was significant. In the case of Comparative Example 3, since the content of the isophthalic acid component was high and the crystallinity was low, the resin was soft and the applied force was insufficient in the stretching, and thus the unevenness in thickness was significant. Comparative Example 4 was an experiment replicating the contents described in Patent Document 1, and since the TS3 temperature was low, the refractive index in the thickness direction was low and the lamination strength was insufficient.
- Comparative Example 5 was an experiment replicating the contents described in Patent Document 2, and since the TD stretching temperature was low and there was no cooling step after the heat fixation, the unevenness in thickness was significant due to abrupt cooling.
- Comparative Example 6 was an experiment replicating the contents described in Patent Document 3, and the MD stretching was carried out in three stages. In Comparative Example 6, the extrusion temperature was as high as 310°C, and therefore, the intrinsic viscosity of the film became low, relaxation in the heat fixation was insufficient, and the thermal shrinkage rate was high.
- Comparative Example 7 was an experiment replicating the contents described in Patent Document 4, and since there was no cooling step after the heat fixation, the unevenness in thickness was significant due to abrupt cooling.
- Comparative Example 8 since no recycled raw materials derived from PET bottles were used, gradual cooling was performed by lowering the TS3 temperature to make the unevenness in thickness slight. However, due to an insufficient temperature for TS3, the refractive index in the thickness direction was low, and the lamination strength was insufficient.
- the present invention it is made possible to provide a polyester film containing a polyester resin obtained by recycling high-quality PET bottles, and more particularly, it is made possible to provide a polyester film containing a polyester resin obtained by recycling PET bottles and having low thermal shrinkage, high lamination strength, and slight unevenness in thickness.
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Claims (2)
- Film de polyester étiré biaxialement, comprenant 50% en poids ou plus et 95% en poids ou moins d'une résine de polyester obtenue par recyclage de bouteilles en PET, le film de polyester satisfaisant les exigences suivantes :(1) la teneur en composant acide isophtalique de tous les composants acides dicarboxyliques dans toute la résine de polyester qui compose le film de polyester est de 0,5% en mole ou plus et de 5,0% en mole ou moins ;(2) la viscosité intrinsèque de la résine qui compose le film de polyester est de 0,64 dl/g ou plus et de 0,80 dl/g ou moins ;(3) le taux de rétrécissement thermique à 150°C dans la direction longitudinale et dans la direction transversale est de 0,1% ou plus et de 1,5% ou moins ;(4) l'indice de réfraction du film de polyester dans la direction de l'épaisseur est de 1,4930 ou plus et de 1,4995 ou moins ; et(5) l'irrégularité de l'épaisseur calculée selon l'équation suivante est de 16% ou moins dans les deux directions longitudinale et transversale, dans le cas où chaque épaisseur Tn (n = 1 à 200) (unité : µm) d'un film de 1 m de long sur 1 m de large est mesurée tous les 5 mm et au niveau de 200 points, et l'épaisseur maximale est définie comme étant Tmax, l'épaisseur minimale est définie comme étant Tmin, et l'épaisseur moyenne est définie comme étant Tmoy :
- Film de polyester selon la revendication 1, ledit film de polyester contenant 0,01% en poids ou plus et 1% en poids ou moins de particules inorganiques.
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JP2012214141 | 2012-09-27 | ||
PCT/JP2013/075808 WO2014050844A1 (fr) | 2012-09-27 | 2013-09-25 | Film de polyester |
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EP2868688A1 EP2868688A1 (fr) | 2015-05-06 |
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EP (1) | EP2868688B1 (fr) |
JP (2) | JP5500327B1 (fr) |
KR (1) | KR101530840B1 (fr) |
CN (1) | CN104603186B (fr) |
PL (1) | PL2868688T3 (fr) |
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WO (1) | WO2014050844A1 (fr) |
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JP6167798B2 (ja) * | 2012-09-27 | 2017-07-26 | 東洋紡株式会社 | ポリエステルフィルム |
JP6167797B2 (ja) * | 2012-09-27 | 2017-07-26 | 東洋紡株式会社 | ポリエステルフィルム |
JP6500629B2 (ja) * | 2015-06-19 | 2019-04-17 | 東洋紡株式会社 | 積層フィルム |
JP6728605B2 (ja) * | 2015-09-18 | 2020-07-22 | 大日本印刷株式会社 | 積層体 |
WO2017159582A1 (fr) | 2016-03-18 | 2017-09-21 | 東洋紡株式会社 | Film de polyester, stratifié, et corps d'emballage |
WO2018021211A1 (fr) * | 2016-07-27 | 2018-02-01 | 東洋紡株式会社 | Film de polyester blanc, stratifié et sachet d'emballage |
JP7071705B2 (ja) * | 2017-07-27 | 2022-05-19 | 大日本印刷株式会社 | 積層体 |
PL3565718T3 (pl) * | 2017-10-31 | 2022-01-31 | Flex Films (Usa) Inc. | Termoplastyczne folie o małym śladzie węglowym zawierające poddane recyklingowi materiały |
JP7103013B2 (ja) * | 2018-07-20 | 2022-07-20 | 東洋紡株式会社 | 空洞含有ポリエステル系樹脂フィルム |
CN109162456A (zh) * | 2018-08-07 | 2019-01-08 | 上海建工七建集团有限公司 | 一种对拉螺栓套管结构、模板固定结构及使用方法 |
JP6642748B2 (ja) * | 2019-02-05 | 2020-02-12 | 東洋紡株式会社 | 積層フィルム |
CN113453870B (zh) * | 2019-02-18 | 2023-04-18 | 东洋纺株式会社 | 双轴拉伸聚酯膜卷 |
JP7484928B2 (ja) | 2019-10-31 | 2024-05-16 | 東洋紡株式会社 | 熱収縮性ポリエステル系フィルムロール |
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JPWO2021241145A1 (fr) * | 2020-05-29 | 2021-12-02 | ||
EP4257351A1 (fr) | 2020-12-02 | 2023-10-11 | Toyobo Co., Ltd. | Film transparent barrière au gaz |
CN114591604B (zh) * | 2020-12-07 | 2024-08-20 | 爱思开迈克沃有限公司 | 聚酯薄膜、保护薄膜及其制备方法 |
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JPH07114721A (ja) | 1993-10-18 | 1995-05-02 | Toray Ind Inc | 磁気記録媒体用ポリエステルフィルム |
JPH1110723A (ja) * | 1997-06-25 | 1999-01-19 | Mitsubishi Kagaku Polyester Film Kk | 二軸延伸ポリエステルフィルムの製造方法 |
JP3518294B2 (ja) | 1997-08-08 | 2004-04-12 | トヨタ自動車株式会社 | 電磁駆動弁 |
EP1033244B1 (fr) * | 1999-03-04 | 2004-02-11 | Teijin Limited | Film stratifié en polyester étiré biaxialement |
JP2001239579A (ja) | 2000-02-28 | 2001-09-04 | Toyobo Co Ltd | インサート成形用二軸延伸ポリエステル系フィルム |
JP5142421B2 (ja) | 2000-06-05 | 2013-02-13 | 東レ株式会社 | 透明蒸着用2軸配向ポリエチレンテレフタレートフィルム |
JP4538578B2 (ja) * | 2002-11-07 | 2010-09-08 | エフテックス有限会社 | ポリエチレンテレフタレート系ポリエステルの熱融着性フィルムおよびその製造方法 |
DE10352432A1 (de) * | 2003-11-10 | 2005-06-09 | Mitsubishi Polyester Film Gmbh | Weiße, heißsiegelbare, peelfähige Polyesterfolie, Verfahren zu ihrer Herstellung und ihre Verwendung |
JP4494080B2 (ja) * | 2004-04-28 | 2010-06-30 | 三菱樹脂株式会社 | 再生ポリエステルシート |
JP5082196B2 (ja) | 2005-03-04 | 2012-11-28 | 東洋紡績株式会社 | 成型用ポリエステルフィルム |
JP2008095084A (ja) * | 2006-09-13 | 2008-04-24 | Toyobo Co Ltd | 成型用ポリエステルフィルム |
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2013
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- 2013-09-25 WO PCT/JP2013/075808 patent/WO2014050844A1/fr active Application Filing
- 2013-09-25 CN CN201380046512.5A patent/CN104603186B/zh active Active
- 2013-09-25 JP JP2013546121A patent/JP5500327B1/ja active Active
- 2013-09-25 US US14/418,273 patent/US9296868B2/en active Active
- 2013-09-25 PL PL13841399T patent/PL2868688T3/pl unknown
- 2013-09-25 EP EP13841399.2A patent/EP2868688B1/fr active Active
- 2013-09-26 TW TW102134726A patent/TWI633993B/zh active
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2014
- 2014-03-10 JP JP2014046242A patent/JP6206260B2/ja active Active
Also Published As
Publication number | Publication date |
---|---|
JP6206260B2 (ja) | 2017-10-04 |
TW201420315A (zh) | 2014-06-01 |
CN104603186B (zh) | 2016-08-24 |
EP2868688A4 (fr) | 2015-05-20 |
US9296868B2 (en) | 2016-03-29 |
PL2868688T3 (pl) | 2017-01-31 |
JP2014111790A (ja) | 2014-06-19 |
EP2868688A1 (fr) | 2015-05-06 |
JP5500327B1 (ja) | 2014-05-21 |
JPWO2014050844A1 (ja) | 2016-08-22 |
CN104603186A (zh) | 2015-05-06 |
KR20150017778A (ko) | 2015-02-17 |
KR101530840B1 (ko) | 2015-06-22 |
US20150259484A1 (en) | 2015-09-17 |
WO2014050844A1 (fr) | 2014-04-03 |
TWI633993B (zh) | 2018-09-01 |
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